Single-Step Functionalization Strategy of Graphene Microtransistor Array with Chemically Modified Aptamers for Biosensing Applications.

Graphene solution-gated field-effect transistors (gSGFETs) offer high potential for chemical and biochemical sensing applications. Among the current trends to improve this technology, the functionalization processes are gaining relevance for its crucial impact on biosensing performance. Previous efforts are focused on simplifying the attachment procedure from standard multi-step to single-step strategies, but they still suffer from overreaction, and impurity issues and are limited to a particular ligand. Herein, a novel strategy for single-step immobilization of chemically modified aptamers with fluorenylmethyl and acridine moieties, based on a straightforward synthetic route to overcome the aforementioned limitations is presented. This approach is benchmarked versus a standard multi-step strategy using thrombin as detection model. In order to assess the reliability of the functionalization strategies 48-gSGFETs arrays are employed to acquire large datasets with multiple replicas. Graphene surface characterization demonstrates robust and higher efficiency in the chemical coupling of the aptamers with the single-step strategy, while the electrical response evaluation validates the sensing capability, allowing to implement different alternatives for data analysis and reduce the sensing variability. In this work, a new tool capable of overcome the functionalization challenges of graphene surfaces is provided, paving the way toward the standardization of gSGFETs for biosensing purposes.

Molecular-Level Insights on Reactive Arrangement in On-Surface Photocatalytic Coupling Reactions Using Tip-Enhanced Raman Spectroscopy.

Plasmon-enhanced photocatalytic coupling reactions have been used as model systems in surface-enhanced Raman spectroscopy and tip-enhanced Raman spectroscopy (TERS) research for decades. However, the role of reactive arrangement on efficiency of these model reactions has remained largely unknown to date often leading to conflicting interpretations of experimental results. Herein, we use an interdisciplinary toolbox of nanoscale TERS imaging in combination with molecular-resolution ambient scanning tunnelling microscopy (STM) and density functional theory (DFT) modeling to investigate the role of reactive arrangement in photocatalytic coupling of 4-nitrobenzenethiol (4-NTP) to p,p'-dimercaptoazobisbenzene on single-crystal and polycrystalline Au surfaces for the first time. TERS imaging with 3 nm resolution clearly revealed a significantly higher catalytic efficiency inside a kinetically driven disordered phase of the 4-NTP adlayer on Au compared to the thermodynamically stable ordered phase. Furthermore, molecular level details of the self-assembled structures in the disordered and ordered phases obtained using ambient high-resolution STM enabled an unambiguous structure-reactivity correlation of photocatalytic coupling. Finally, quantitative mechanistic insights obtained from DFT modeling based on the accurate parameters determined from STM imaging emphatically confirmed that a combination of steric hindrance effect and energetic barrier leads to a lower reaction efficiency in the ordered phase of the 4-NTP adlayer. This fundamental study establishes the first direct structure-reactivity correlation in photocatalytic coupling and highlights the critical role of reactive arrangement in the efficiency of on-surface coupling reactions in heterogeneous catalysis at large.

Ethanol Solvation of Polymer Residues in Graphene Solution-Gated Field Effect Transistors.

The persistence of photoresist residues from microfabrication procedures causes significant obstacles in the technological advancement of graphene-based electronic devices. These residues induce undesired chemical doping effects, diminish carrier mobility, and deteriorate the signal-to-noise ratio, making them critical in certain contexts, including sensing and electrical recording applications. In graphene solution-gated field-effect transistors (gSGFETs), the presence of polymer contaminants makes it difficult to perform precise electrical measurements, introducing response variability and calibration challenges. Given the absence of viable short to midterm alternatives to polymer-intensive microfabrication techniques, a postpatterning treatment involving THF and ethanol solvents was evaluated, with ethanol being the most effective, environmentally sustainable, and safe method for residue removal. Employing a comprehensive analysis with XPS, AFM, and Raman spectroscopy, together with electrical characterization, we investigated the influence of residual polymers on graphene surface properties and transistor functionality. Ethanol treatment exhibited a pronounced enhancement in gSGFET performance, as evidenced by a shift in the charge neutrality point and reduced dispersion. This systematic cleaning methodology holds the potential to improve the reproducibility and precision in the manufacturing of graphene devices. Particularly, by using ethanol for residue removal, we align our methodology with the principles of green chemistry, minimizing environmental impact while advancing diverse graphene technology applications.

Oligonucleotide microarray design for detection and serotyping of human respiratory adenoviruses by using a virtual amplicon retrieval software.

The rapid development of new molecular biology methods has improved infectious disease diagnosis, which is increasingly important to clinical management and public health. A wide variety of new methods which are more specific, sensitive and robust, such as combination of PCR and microarray technology, has gradually replaced the conventional assays usually used in routine diagnosis. Both methods have the advantage of speed and sensitivity but tend to be expensive and technically demanding. Therefore, it is necessary to develop more simple assays that could be available for all diagnostic laboratories. To this aim, a simple microarray assay for detection and typing of adenoviruses causing acute respiratory disease in humans was developed. The absence of effective therapeutic or alternative prophylactic treatment for this infection makes essential its rapid diagnosis to implement fast control measures. Moreover, the family Adenoviridae includes numerous serotype groups and constitutes an ideal model system to develop diagnostic methods for other human pathogens. For their precise identification, an amplicon retrieval software that simplifies and accelerates the processing of all sequences necessary to perform this type of experiments has also been developed. This new technology was applied for the simultaneous detection and serotyping of acute respiratory disease-causing adenoviruses in laboratory and clinical samples with efficiency and accuracy.